Catalytic Reduction of ortho- and para-Azidonitrobenzenes via tert-Butoxide Ion Mediated Electron Transfer

Abstract

The reduction of a range of substituted azidonitrobenzene derivatives to the corresponding aniline is described. The chemoselective reaction proceeds cleanly and in good yield, generating minimal waste products. The process involves a thiazolium salt derived species which is proposed as a radical anion relay, with tert-butoxide as the stoichiometric reductant.

Key words

azide - reduction - tert-butoxide - electron transfer - N-heterocyclic carbene

• References and Notes

• 1a Scriven EF, Turnbal K. Chem. Rev. 1988; 88: 297
• 1b Bräse S, Gil C, Knepper K, Zimmermann N. Angew. Chem. Int. Ed. 2005; 44: 5188
• 2 Bräse S, Banert K In Organic Azides: Syntheses and Applications . Bräse S, Banert K. Wiley; Chichester: 2010
• 3a Kolb HC, Finn MG, Sharpless KB. Angew. Chem. Int. Ed. 2001; 40: 2004
• 3b Meldal M, Tornøe CW. Chem. Rev. 2008; 108: 2952
• 3c Moses JE, Moorhouse AD. Chem. Soc. Rev. 2007; 36: 1249
• 4a Schilling CI, Jung N, Biskup M, Schepers U, Bräse S. Chem. Soc. Rev. 2011; 40: 4840
• 4b Hong V, Presolski SI, Ma C, Finn MG. Angew. Chem. Int. Ed. 2009; 48: 9879
• 5 Binder WH, Sachesenhofer R. Macromol. Rapid Commun. 2007; 28: 15
• 6a Kolb HC, Sharpless KB. Drug Discov. Today 2003; 8: 1128
• 6b Moorhouse AD, Spiteri C, Sharma P, Zloh M, Moses JE. Chem. Commum. 2011; 47: 230
• 6c Moorhouse AD, Santos AM, Gunaratnam M, Moore M, Neidle S, Moses JE. J. Am. Chem. Soc. 2006; 128: 15972

For some selected publications regarding the radical chemistry of azides, see:
• 7a Benati L, Montevecchi PC. J. Org. Chem. 1981; 46: 4570
• 7b Kim S, Joe GH, Do JY. J. Am. Chem. Soc. 1994; 116: 5521
• 7c Montevecchi PC, Navacchia ML, Spagnolo P. Eur. J. Org. Chem. 1998; 1219
• 7d Benati L, Leardini R, Minozzi M, Nanni D, Spagnolo P, Strazzi S, Zanardi G. Org. Lett. 2002; 4: 3079
• 7e Renaud P, Olliver C. J. Am. Chem. Soc. 2001; 123: 4717
• 7f Renaud P, Olliver C, Panchaud P. Angew. Chem. Int. Ed. 2002; 41: 3460
• 8a Barral K, Moorhouse AD, Moses JE. Org. Lett. 2007; 9: 1809
• 8b Moorhouse AD, Moses JE. Synlett 2008; 2089
• 8c Zhang F, Moses JE. Org. Lett. 2009; 11: 1587
• 8d Sharma P, Moorhouse AD, Moses JE. Synlett 2011; 2384
• 9 Warrier M, Lo MK. F, Monbouquette H, Garcia-Garibay MA. Photochem. Photobiol. Sci. 2004; 3: 859
• 10 Herbranson DE, Hawley MD. J. Org. Chem. 1990; 55: 4297
• 11 Gartiser T, Selve C, Delpuech J.-J. Tetrahedron Lett. 1983; 24: 1609
• 12 Boyer JH. J. Am. Chem. Soc. 1951; 71: 5865
• 13 Rolla F. J. Org. Chem. 1982; 47: 4327
• 14a Hays DS, Fu GC. J. Org. Chem. 1998; 63: 2796
• 14b Benati L, Bencivenni G, Leardini R, Minozzi M, Nanni D, Scialpi R, Spagnolo P, Zanardi G. J. Org. Chem. 2005; 70: 3046
• 15 Benati L, Bencivenni G, Leardini R, Minozzi M, Nanni D, Scialpi R, Spagnolo P, Zanardi G. J. Org. Chem. 2006; 71: 5822
• 16 Staudinger H, Meyer J. Helv. Chim. Acta 1919; 2: 635
• 17a Guthrie RD, Nutter DL. Bull. Soc. Chim. Belg. 1982; 91: 455
• 17b Guthrie RD, Nutter DL. J. Am. Chem. Soc. 1982; 104: 7478
• 18 Guthrie RD. J. Org. Chem. 1975; 40: 402
• 19 Russel GA, Janzen EG, Strom ET. J. Am. Chem. Soc. 1964; 86: 1807
• 20 Inoue H, Higashiura K. J. Chem. Soc., Chem. Commun. 1980; 549
• 21 No reduction product was observed when the reaction mixture was heated at 50 °C.
• 22a Khramov DM, Bielawski CW. Chem. Commum. 2005; 4958
• 22b Khramov DM, Bielawski CW. J. Org. Chem. 2007; 9407
• 22c Coady DJ, Khramov DM, Norris BC, Tennyson AG, Bielawski CW. Angew. Chem. Int. Ed. 2009; 48: 5187
• 23a Canal JP, Ramnial T, Dickie DA, Clyburne JA. C. Chem. Commun. 2006; 1809
• 23b Hahn FE. Angew. Chem. Int. Ed. 2006; 45: 1348
• 23c Crabtree RH. J. Organomet. Chem. 2005; 690: 5451
• 23d Herrmann WA, Köcher C. Angew. Chem., Int. Ed. Engl. 1997; 36: 2162
• 23e Arduengo AJ. III. Acc. Chem. Res. 1999; 32: 913
• 23f Bourissou D, Guerret O, Gabbaï FP, Bertrand G. Chem. Rev. 2000; 100: 39
• 24 Chen Y, Kamlet AS, Steinman JB, Liu DR. Nat. Chem. 2011; 3: 146
• 25 Maejima T, Shimoda Y, Nozaki K, Mori S, Sawama Y, Monguchi Y, Sajiki H. Tetrahedron 2012; 68: 1712